Textile printing pastes and method of applying



United States Patent TEXTILE PRINTING PASTES AND METHOD OF APPLYINGHelmut Kleiner, Opladen, Otto Bayer, Leverkusen-Bayerwerk, and BennoBecht, Munich, Germany, assignors to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a corporation of Germany NoDrawing. Application June 29, 1953, Serial No. 364,952

Claims priority, application Germany August 3, 1949 Claims. (Cl. 117-63)The present invention relates to improvements in the printing and dyeingof textiles of any kind with pigment dyestuffs and more particularly toa novel printing paste.

This application is a continuation in part of our copending applicationSer. No. 117,262, filed September 22, 1949, now Patent 2,643,958.

According to the hitherto known processes for printing and dyeingtextiles with pigments, for the most part ready made film-formingcompositions are used as binders. These binders have to be waterinsoluble in order to ensure fixation of the pigments that is fast towashing. Therefore, the film-forming agents must be employed in theprinting or padding pastes either in the form of a solution in organicsolvents or in the form of an aqueous suspension or emulsion in a mixedaqueousorganic medium. The additional use of organic solvents causesmany inconveniences in print and dye works. On the other hand, printingor padding pastes containing film-forming agents in the form of pureaqueous emulsions are only insufficiently stable and, furthermore,

have the disadvantage that the binder does not pene-- trate sufiicientlydeeply into the fiber, as these emulsions are broken immediately oncontacting the fabric, the fastness properties being impaired thereby.

It has also been proposed to produce a film-forming agent on the fiber,viz. from components which are added 7 to the printing pastes or paddingsolutions in a watersoluble condition, for instance, from phenol andformaldehyde. Films thus obtained, however, possess poor mechanicalproperties. In particular they are too brittle and in consequencethereof fastness to rubbing is poor. Furthermore, film-formingcompositions of this kind can be obtained only under very severeconditions. Such processes, therefore, have not proved to be useful inpractice.

It is therefore an object of our invention to provide a binding agentfor the pigment or dyestuff soluble in aqueous printing or paddingpastes.

A further object resides in the provision of binding agents readilyconvertible into insoluble, supple and elastic films on the fibrousmaterial.

Another object is to provide a printing paste which will fix the pigmenton the fabric fast to washing and which will not impair the feel or handof the goods.

A still further object of the'invention is to provide a process ofdecorating textile fabrics.

Still further objects will become apparent as the followingspecification proceeds.

The object osf the invention are accomplished by using as a printingpaste a composition having the following characteristics:

(a) As film-forming compositions, resinous polyamines having recurringbasic radicals selected from the group consisting of primary andsecondary amino groups, which polymers are water soluble per se or'inthe form of their salts with acids,

tion which is fast to washing, acids and alkalies.

(b) They are present in printing and padding pastes in form of 'suchsalts in aqueous solutions,

(0) The printing and padding pastes, furthermore, contain polyfunctional compounds capable of reacting with amino or imino groups(hereinafter called cross-linking agents), which at normal temperaturesare at least difiicultly soluble in water and are finely distributed inthe printing or padding pastes.

Printing or padding pastes prepared according to the foregoing recipeand containing apart from the pigment dyestuffs the usual additions,such as thickening agents, glycerine etc., are stable at ordinarytemperature for some, days, or even for some Weeks, which renders themsuitable for practical application in print and dye works. Theirstability is due to the fact that the reactivity of the polymerscontaining aminoor imino groups is checked by salt formation with theacids. The stability of such printing or padding pastes, however, can beovercome in a simple way as soon as they have been applied to thetextiles to be printed or dyed. The printed or padded material, forinstance, can be subjected to an alkaline aftertreatment. By thistreatment the film-forming compositions on the. fiber are set free fromtheir salts in an insoluble state, and by liberating the basic groupsthe conditions are provided for the additional cross-linking reactionwith the compounds described (sub c).

Another processing method of our invention consists in employing theresinous polyamines in form of their ting ,free the basic groups providethe conditions required for cross-linking. Which way is the betterdepends on the special conditions of the printing or dyeing processconcerned. For instance, preference is given to the alkalinedevelopment, if. printing is effected in combination with dyestuffsother than pigments, for in- -stance, vat of coupling dyes which per serequire an "alkaline aftertreatment, or if a wet operation is neces saryfor achieving a special finishing effect.

As volatile acids, acetic acid and formic acid are preferred.

The process according to the present invention combines the advantagesof the known processes referred to above without exhibiting thedisadvantages thereof. The use of organic solventscan be dispensed withand the process can be performed in a purely aqueous medium. Thefilm-forming compositions are soluble in the aqueous printing or paddingpastes and, therefore, easily penetrate the fiber. Furthermore, theybecome insoluble by the alkaline aftertreatment or heating in thepresence of cross-linking agents and consequently insure a fixa- Despitethe cross-linking the film-forming compositions are distinguished bygood elasticity and suppleness, properties characteristic for polyvinylester, so that a good fastness-to rubbing is guaranteed and the feel ofthe fibrous material is not impaired. Fixing by drying already takesplace at moderate temperatures of, for instance, about 6080 C. within afew minutes. Fixing by an alkaline aftertreatnzent is also carried outwithin a few minutes.

Such compounds are suitableas binders as contain two or more primary orsecondary amino-groups and are just soluble in water per se or in theform of their salts, their solubility being so adjusted that it can beremoved easily and completely by a cross-linking-reaction. 7

It is necessary to produce an insoluble, high molecular weight form onthe textile material, which should preferably also be fixed in thetextile material. Reaction componentsshould therefore be used, which arenot too macromolecular; since compounds of too high a molecular weightdo not penetrate sufficiently into the textile material.

The effect desired may be obtained with various poly amines and variouscross-linking-agents." Of the polyamines those having a comparativelyhigh molecular weight possess the solubility characteristics mentionedabove. As a lower limit a minimum molecular weight of about 200 appearsnecessary. The maximum molecular weight is limited by the beginninginsolubilization of the macromolecular polyamine. The molecular weightand reactivity of each polyamine should be adjusted to the molecularweight and reactivity of each cross-linking agent. If the polyamine forinstance has a low molecular weight and only a few reactive groups thecross-linking agent should have a great number of reactive groups. Inthose cases where the amine has the character of a macromolecularcompound fewer or less active reactive groups in the cross-linking agentare sufficient. Polymeric amines obtained by polymerization arepreferred.

- Obviously, the resinous polyamine should be free from groups otherthan the primary or secondary amino groups, which other groups wouldpreferentially react with the polyfunctional compound, since suchreaction would im pair the desired cross-linking reaction of the aminogroups.

Among the resinous polyamines suitable as binders according to ourinvention are the polymeric esters containing aminoor imino groups,preferably those derived from acrylic or methacrylic acid ester.Naturally further components, such as vinyl esters, styrene orbutadiene, may be copolymerized therewith. Furthermore, copolymers ofother esters, for instance fumaric or maleic acid ester, with the abovepolymerization components may be employed. The amino or imino groups canbe introduced into the polymeric esters in various ways. For instance,acrylic ester may be subjected to copolymerization with acrylonitrile,and the nitrile groups, of the polymer then totally or partly reduced toamino groups. consists in copolymerizing acrylic ester with acrylamide,adding the copolymer obtained to an acrylonitrile polymer and thenreducing the nitrile group to an amino group. Other possibilitiesconsist inreacting polyacrylic ester and ethanol amine and addingacrylonitrile or cyanoethyl isocyanate or ethylene imine to thehydroxyethyl amide groups obtained, amino groups being formed eitherdirectly or after subsequent reduction. Still another possibilityconsists in first partially saponifying the polyacrylic ester and thencausing it to react with cyano-ethyl-isocyanate. In this case acarbonamide link is formed with the evolution of carbon dioxide, thecyano group introduced being later reduced to an amino group. Aparticularly simple method for the production of the starting'materialsconsists in condensing polymers containing ester groups with biorpolyfunctional amines, such as ethylene diamine, diethylene triamine,tetramethylene diamine, hexamethylene diamine, N-methylpropylenediamine, N-isobutylpropylene diamine and diamines with hetero-atoms o'rhetero groups, such as diamino dipropylether, until 1 a state is reachedwhere the components are already chemically combined but are stillsoluble in aqueous acids or organic solvents or fusible. Thisintermediate stage can easily be maintained. Preferably the componentsare heated in the presence of an organic solvent for this purpose.

Basic groups may be introduced into the polymers in various ways, forinstance by polymerizing therewith compounds capable of reaction withdior polyamines in such a manner that basic groups remain in the finalproduct. As an example of the many possibilities may be mentioned theinterpolymerization of styrene and acrylfluoride andthe subsequentreaction of the interpolymer with adiamine, for instancemethyl-propylene-diamine, in the molecular proportion 1:1.

\ Furthermore polymers containing groups capable of Another wayreduction or hydrogenation, for instance, nitroor nitrile groups may beconverted into basic polymers by the action of nascent or catalyticallyactivated hydrogen.

According to Patent No. 2,122,707 it is possible to renderpolyvinylmethylketones basic and watersoluble by reaction with ammonia.These basic resins may be made insolubleby heating; If they arecross-linked with bifunctional compounds according to the presentinvention they can be fixed much more quickly and much more effecivelyFurthermore polyacrylic acid nitrile may be converted into water-solublederivatives-probably basic amidines by the action of boiling polyamines,for instance ethylene diamine.

Polyvinylamines may be obtained by saponification of polymeric vinylsuccinirnide or vinyl phthalimide by means of hydrazine hydrate,preferably according to the process of Reynolds (JIAm. Chem. Soc. 69/4,page 911).

Basic polyesters may be obtained from isocyanate modified polyesters asthey are for instance described in the co-pending application Serial No.70,598 filed January 12, 1949, by Miiller et al., now abandoned, byreaction with dior polyamines.

- Furthermore all those high molecular weight compounds are suited forthe process according to the invention in which halogen atoms may beexchanged for amino groups, for instance, in chlorinatedpolyisobutylenes, chlorinated parafiin hydrocarbons with about 12-20carbon atoms.

A further class of compounds which may be employed according to thepresent invention are the polyimines, i. e. compounds which containimino groups in their chain and which are accessible in various ways,for instance polyethylene imine may be obtained by polymerization ofethylene imine. By condensation of ethylene chloride with ammoniasimilar polyimines are accessible.

The basic, polymeric compounds containing epoxy and -NH and/ or NHzgroups in their molecule which are obtainable by reaction ofepichlorohydrin or butylene dioxide and similar alkylene oxides Withammonia or primary or secondary amines may also be employed as basicpolymers according to thisinvention.

Furthermore basic polyamides may be mentioned as suitable binders. Theymay be obtained by the reaction of dior polycarboxylic acids containingimino groups or their esters with dior polyamines or of dior polyaminescontaining imino groups with dior polycarboxylic acids or their esters.As an example of the first named principle of reaction the condensationproduct from iminodipropionic acid and ethylenediamine may be mentioned:

-CO (CH2 2NH (CH2) 2CONH(CH2 2 NH-CO(CH2) zNH (CH2) 2CONH(CH2 2NH- Forthe second named group of compounds the reaction products of oxalic acidester with diethylene triamine may be taken as an example.

Similarly basic polyurethanes may be employed according to the inventionsuch as they are for instance obtained from N-acetyl-diethanolamine andhexamethylene diisocyanate with subsequent splitting off of the acetylgroup.

Furthermore basic polyureas may be used as basic polymers. Thesepolyureas are obtainable, for instance, by reacting a diprimaryaliphatic polyamine containing NH groups in its molecule with adiisocyanate. As diprimary aliphatic polyamines, diethylene triarnine,triethylene tetramine, dipropylene triamine, wy diamino dipropyl ether,diaminodipropyl tetramethylene diamine (Spermin),*yyy'-diamino-propylmethylamine etc. may be employed, Tetramethylenediisocyanate, hexamethylene diisocyanate and other polymethylenediisocyanatesare preferably used as diisocyanates in carrying out the:re.- action.

Long chain compounds containing imino groups may also be obtained bylinking high molecular polyamines. Thus, polybasic compounds such as areobtained bythe addition of bifunctional amines to acrylonitrile andsubsequent hydrogenation, maybelinked to yield long chain compounds byreaction with diisocyanates, dicarboxylic acids, dichlorides,diacrylamides etc. For instance hexamethylene diamine is added toacrylonitrile on both sides and hydrogenated. The addition of thereaction product to a further acrylonitrile molecule and subsequenthydrogenation is repeated several times until thedesired prod uct isobtained.

which for instance may be prolonged by further reaction with one of thefollowing bifunctional compounds:

(at) Oxalylchloride, oxalic acid ester or the like (b) Diisocyanates,for instance hexanediisocyanate v (c) Diacrylamides, for instanceN-methyldipr'opylehetriamine diacrylamide. I?

hydro-1,3,5 -triacrylyl-s-tri-azine) having the following probableformula:

CHg

N-C O-OH-CH:

CHFCHC O-N Furthermore the following compounds may be employed as basicbinders: basic polysaccharides, for instance so-called amine cellulose,addition products of ethylene imine and cellulose, hydrolysates ofprotein substances, for instance hydrolysates from glue, casein orgelatine, and aminolysates with polyamines.

Further monomeric polyamines which are suitable as binders are thehydrogenation products of compounds obtained by the reaction of thehydrogenation product of the compound obtained by the reaction ofpentaerythrite and four mols of acrylonitrile, acrolein and ammoniaoramines, the reaction product of the acetal of chloroacetaldehyde andammonia, the reaction products of glycerol-tri-sulfuric-acid-ester andammonia, the polyamines obtained by the reaction of dior triallylaminewith ammonia in the presence of sodium etc.

The binders may be used as freebases'in aqueous or substantially aqueoussolutio Preferably, however, the aqueous solutions of their salts areemployed in order not to impair the stability of the treating solutions(printing pastes, slopping pastes, impregnating solutions etc.) bypremature reaction of the bases with the polyfunctional compounds. Thesalts of volatile acids are especially suitable as the volatile acidsevaporate during the drying of the impregnated textiles andcross-linking starts immediately. Non-volatile acids may be employed ifthe basic groups are set free by an alkaline after-treatment, es-

pecially in those cases, Where an alkaline after-treatment is necessaryin the course of the printing or dyeing process.

As polyfunctional cross-linking agents compounds may be employed whichcontain two or more radicals capable of reaction with primary orsecondary amino groups.

formula:

Suitable compounds are for instance the so-calledpolyisocyanate-formers. By' polyisocyanate-formers compounds areunderstood, which react like polyfunctional isocyanates at elevatedtemperatures (cf. French- Patent 876,285). As examples may be namedaddition products of one mol of a diisocyanate and two mols of a1.3-diketone or 1.3-ketone ester like acetic acid ester or maleic acidester. Especially well suited are the addition products of bisulfitesand polyfunctional isocyanates which .possess the advantage of beingWater soluble,

Further cross-linking agents are those compounds containing at leasttwocarboxylic acid groups (or salts thereof, for instance, ammonium salts),carboxylic acid halide groups, carbonamide groups, carboxyalkyl orcarboxyaryl group's, hydroxymethyl groups, a lkoxy methyl groups or acombination of these groups. Examples of these compounds are: oxalicacid (or their salts), succinic acid, adipic acid, sebacic acid,-adipicacid dichloride, cyanuric chloride, oxalamide, succinimide, dimethyloxalate, diethyl malonate, diethyl adipate,methane-tricarboxylic-acid-diphenylester,-N-cyano-imino-dicarboxylic-acid=diphenylester, the condensation productof phenoxy-acetic acicLwith formaldehyde, hexamethylol melamine orits=ethers,- the soluble reaction product of di'cyandiamide withformaldehyde (German Patent 671,704). In addition, polymeric productscontaining a plurality of the above substituents may be used, forinstance: polyacrylates, polyacrylamides, polymethylolpolyacrylamides,acid polyesters from three mols of maleic acid anhydride and one mol ofglycerol. As cross-linking agents theremay also be employed con lpoundscontaining at least two epoxy groups or ethylene imine groups, forinstance:

The reaction productof one mol cyanuric chloride with three mols ofethyleneimine having the following GE's- 0112 Thereaction product ofhexahydro-1,3,5-tricrylyl-stria zine' and two or three mols of ethyleneimine,-reaction products of phosphoric acid-alkylester-dichlorides andethylene imine, reaction products of disulfochlorides and ethyleneimine, for instance of m-phenylene-disulfochloride and two mols ofethylene imine. Furthermore, bis-epoxypropyl ether, butylene dioxide,the reaction product of novolacs with epichlorohydrin, quaternarycompounds from fglycerol-chloroacetic acid ester and three mols of theaddition product of epichlorohydrine and dimethylamine of the formula:

Furthermore compounds with at least two olefinic double bonds may beused as cross-linking agents, for

instance, hexahydro-l,3,S-triacrylyl-s-triazine, allylstarch etc. 1 a

When volatile acids'are employed we have found that the volatile acidsare preferably used in an amount in excess of that necessary fordissolving the resinous polyamines. Stability of the printing andpadding pastes is improved thereby.

Our present invention is further illustrated by the fol Example 1 1000parts of acrylic acid butyl ester are diluted with 1000 parts of butanoland polymerized at 100 C. with the addition of 0.5% of benzoyl peroxide.The polymerizate thus obtained is heated to the boil in a 50% butanolsolution with 1-amino-3-methylamine propane (the ratio of the diamine toone ester group being 1:1), until a sample has become soluble in diluteacetic acid, about 18 hours being required therefor. After separatingthe solvent and the non-reacted amine the residue is washed with Waterand dissolved in dilute acetic, acid with an excess of about 20% of thecalculated amount of acid to yield a 40% aqueous viscous solution.

A printing paste containing:

is printed upon a cotton fabric. After printing it is dried and thefabric is exposed to a temperature of 60-100 C. for -5 minutes. Besidesa good feel, the printing design thus obtained exhibits excellentfastness properties.

Example 2 A fixation of pigments according to the pad-dyeing processwhich is fast to washing is accomplished in the following manner:

50 parts of tragacanth thickening 6521000 are stirred 1 with 50 parts ofthe acetic acid solution of the basic ester as described in Example land10 parts of hexahydro- 1,3,S-triacrylyl-s-triazine into a level pasteand diluted with 390 parts of cold water. About 10 parts of a pigmentdyestuff paste are stirred with 400 parts of water and added to thefirst solution through a fine hair sieve. A mixed fabric of cotton andviscose rayon is passed through this padding liquor on a two-bowlpadding machine, dried and heated as described in Example 1. A dyeing isobtained with a good handle, excellent levelling and fastness. Theresistance of the fabric to abrasion is improved by the pad-dyeing.

Example 3 The following resist is printed on cotton fabrics:

300 parts of tragacanth 6521000 200 parts of the acetic acid solution ofExample 1 200 parts of a 20% pigment dyestuff paste 16 parts of powderedhaxahydro-l,3,S-triacrylyl-s-triazine parts of anhydrous sodium acetateparts of zinc oxide 170 parts of water.

. t 6 It is then briefly dried and slop-padded with the following mix:

Thereafter it is dried, steamed for 5 minutes, washed and soaped withsoda at the boil. Fixation of the binding agent is carried out at thesame time as the developing and fixing of the dyestuff from theleuco-sulfuric acid ester on steaming. According to this method, acolored resist of excellent fastness is obtained.

Example 4 A plastic colored resist under Variamine Blue which is fast towashing is obtained as follows:

(a) Impregnating a fabric with 12 parts of o-oxy-B- naphthoic acidanilide per 1000 parts of water on a twobowl padding machine, drying and(b) Printing with:

350 parts of tragacanth :1000

200 parts of the 40% acetic acid solution of Example 1 200 parts of a20% pigment dyestuff paste 16 parts of finely powderedhexahydro-1,3,5-triacrylyl-striazine 100 parts of lactic acid 100 partsof water,

Drying;

Example 5 A cotton fabric is printed with a mix consisting of:

200 parts of tragacanth 65:1000

200 parts of the 40% acetic acid solution of Example 1 200 parts of a20% pigment dyestuif paste 16 parts of finely powderedhexahydro-l,3,5-triacrylyl-striazine parts of anhydrous sodium acetate'150 parts of zinc oxide 1:1

174 parts of water,

' thereafter dried and the printed fabric is padded on a foulard with apadding solution containing:

parts of aniline hydrochloride 40 parts of tragacanth 651100 5 parts ofaniline dissolved in 200 parts of water 54 parts of potassiumferrocyanide dissolved in 220 parts of water 30 parts of sodium chloratedissolved in 200 parts of Water,

thereafter it is dried and subsequently steamed for 3 minutes in a rapidager and, at last, soaped with soda at the boil. There is obtained acolored resist under aniline black which is distinguished by brilliancy,sharp outlines and excellent fixation of the pigment dyestuff.

Example 6 A colored resist is obtained in the simplest manner byprinting a fabric as described in Example 1, drying, slop-padding andfurther treating as described in Example 2.

Example 7 An interpolymer containing parts of styrene and ten parts ofacrylfiuoride, dissolved in parts of benin 100 parts of butanol. Afterthe reaction is finished the solution is steam-distilled, the residuewashed with water, precipitated from acetic acid solution with soda lye,washed and dried. The material thus obtained contains about two per centbasic nitrogen which can be determined by titration. It is soluble indilute acetic acid with Weak opalescence.

A printing paste containing: 250 parts of tragacanth thickening 6521000400 parts of a 20 per cent, weakly acetic acid solution of "the basicpolystyrene H V, 200 parts of hexahydro-1,3,5-triacryly1-s-triazine 130parts of water r 7 V is printed upon a cotton fabric. After printing,drying follows at 100 C. The printing design thus obtained exhibitsexcellent fastness properties.

An unsized paper foil is immersed in a 20 per cent solution of theacetate .of the basic polystyrene of Example 1, containing '20' percent'of hexahydro-1,3,5- tr'iacrylyl-s-triazine (calculated on theweight of the basic polystyrene) as a cross-linking agent, centrifugedand dried at 80 C. By this treatment the. paper foil has becomeresistant to ink and no flushing occurs.

Example 9 160 parts of a polyester from adipic acid and ethyleneglycolwith an hydroxyl number of 62and an acid num- :be'r of 0.6 is freed fromwater at 130 C. in vacuo and 30 parts of hexanediisocyanate areSadded at100 C. After stirring for an hour (the content .ofJNCQ is- 3.96 per centas calculated) the solution is diluted with 160 parts of chloroform and17 parts of methyl propylenediamine in 100 parts of chloroform areadded. Then the solvent is distilled off and the residue,-contai'ningabout 1.5 per cent of basic nitrogen capable of being determined bytitration, is dissolved in a solution of water and the calculatedquantity of acetic acid to yield a 40 per ,cent paste. f l v Aprintingpaste, containing: e

350 parts of tragacanth thickenin'gr65 :1000

250 parts of a 40 per. cent weakly acetic acid solution of the basicpolyester v, 1 I v 200 parts of a 20 per cent pigment dyestufi paste 20parts of hexahydro 1,3,S-triacrylyl-s-triazine 230 parts of water i l vto light and washing and the material has a-soft hand.

is printed upon a cotton fabric. After printing it is dried Example I 70parts of vinylsuccinimide (M. P. 42 obtained by addition of succinimideto acetylene, are mixed'with 0.5 per cent of benzoylperoxide andpolymerized at 100 C. with cooling. The weakly yellow, brittle polymeris heated for 18 hours to 120" C. with 200 partsofhy- 'drazinehydrate,then, precipitated-and washed with alcohol. The polybasiccompoundobtained is diluted with the calculated quantity of acetic acid to yielda ten per 190 parts bf'iiva'ter f H is printed on a cottonfabrie. Afterprinting the material at 120 C. The printing design'thus obtained isresistant 1 10 is heated for 15 minutes to 100 C. The printing designthus obtained is fast to light and washing.

Example 11 'A polyamine obtained by reaction ofchlorinated'polyisobutylene (with a content of 26 per cent Cl) with am-1nonia under pressure, having a content of about two per cent of basicnitrogen, is dissolved in diluteacetic acid and twelve per cent ofhexahydro-1,3,5-triacry1yl-s-triazine (calculated on the weight of thepolyamine) added. The resultant paste is applied to a staple rayonfabric by slopping. After centrifuging oif the solution it is dried at80 C. The fabric thus treated can be dyed with three per cent of FastW001 Blue BL (Schultz Farbstolftabellen No. 974) in vivid blue.

Example 12 A cotton fabric is printed witha. printing paste of thefollowing composition: 50 parts of polyethyleneimine (50 per cent) arediluted with water to 200 parts. 200 parts offIndahthrenbrown BR(Schlutz Farbstotftabellen No. 1227) (pigment dyestuif paste-20 percent) are stirred into this solution and diluted with 400 parts ofwater. Then 75 parts of acetic acid (50 per cent) and parts of thereaction product of potassium bisulfite and hexanediisocyanate areadded, or instead, 60 parts of formaldehyde (30 per cent),

After printing the material is dried shortly and reacted for fiveminutes at 100 C. A brown print of excellent general fastness propertiesis obtained.

Example 13 I I 15 parts of polyethyleneimine are dissolved in 45 partsof hot water, 30 parts of tragacanth thickening (65: 1000) are stirredinto the solution and the whole'diluted with water to 500 parts. Tenparts of. .I -Ieliogenblue B" (Schultz Farbstotftabellen 7th edition,-Znd'Suppl. Vol., page 195) pigment dyestutf paste20 per cent) are mixedwith 470 parts of water and added to the above solution. Then 25 partsof acetic acid (50 per cent) and 25 parts ofhexahydro-l,3',5-triacrylyl-s-triazine are added. A cotton fabric isdyed with this padding mixture, dried and reacted for five minutes at100 C., a dyeing of excellent uniformity and general fastness propertiesis obtained.

' Example 14 A cotton'fabric is printed with: 50 parts ofpolyethyleneimine (50 per cent), dissolved. in 150 parts .of Water, 50parts of methyl cellulose, 200 parts of Hansayellow Gil (SchultzFarbstofltabellen No. 84) (20 per cent), :lOOparts-of water, parts ofacetic acid (50 per cent), 60 parts of sodium acetate, dissolved in 120parts of water, '130 parts'of zinc oxide'1:1, 65 parts of the reactionproduct of potassium bisulfite and hexanediisocyanate.

After printing the fabric is dried shortly and heated for five'minutesto- 100 C. The material is then passed through a slopped liquorcontaining: parts of anilinechlorohydrate, 40 parts oftragacanth 65:1000, five parts of aniline oi1,.220 parts of water, 54 parts ofpotassium ferrocyanide dissolved in 200 parts of water, 30 parts ofsodiumchlorate, dissolved in 320 parts of water.

After padding the material is dried, treated with steam for threeminutes and oxidized with three grams of potassium bichro'mate and twograms of soda per liter for a minute and a half at 50 C. Then thematerial is rinsed and soaped boiling. In this manner a colored resistunder aniline black with'excellent properties is obtained.

' Example 15 A solution is prepared, containing per liter 50 grams ofthe acetic acid salt "of the addition product of three ,mols ofw.w'-diaminodipropylenediaminobutane (Spermformal), 58 parts of glyoxal(30 per cent) or 45 parts of hexahydro-l,3,5 triacrylyl-s-triazine(dissolved in a mixture of water and acetone). A glass fabric isimpregnated with this solution, centrifuged, and heated for ten minutesto 150 C. The fabric is then dyed in an acetic acid solution with oneper cent of Wool Fast Blue BL (Schultz Farbstofftabellen 1931,,vol. I,No. 974). A fullshade, reddish blue dyeing of excellent fastness towater is obtained.

Example 16 A printing paste containing:

150parts of a basic polyamide, obtained from oxalic aciddiethylester anddipropylenetriamine,

170 parts of acetic acid (30 per cent) 90 parts of water 200 parts of a20 per cent dyestuif paste 350 parts'of tragacanth thickening 65:1000

40 parts of hexahydro-l,3,S-triacrylyl-s-triazine is printed on a cottonfabric. After printing it is dried and heated for five minutes to 100 C.A printing of excellent general properties is obtained.

Example 17 A plastic, colored resist of Variamin-Blue resistant towashing is obtained as follows:

(a) Grounding of a fabric with 12 parts o-hydroxyfi-naphthoic acidanilide per liter on a double-roller-pad ding machine and drying,

(b) Printing with:

350 parts of tragacanth thickening (6511000) 50 parts ofpolyethyleneimine (50 per cent) dissolved in 150 parts of water 200parts of the addition compound of hexamethylenediisocyanate andpotassium bisulfite 100 parts of lactic acid 110 parts of water Example18 A basic polyurea with the viscosity number z1 =230, which is obtainedfrom 0.2 mol of diethylene triarnine, 0.8 mol of yxy diaminopropylrnethylamine and 1.0 mol of hexane diisocyanate, is employed for pigmentprinting in the following paste:

300 parts of a 10% polyurea,

'20 parts of hexahydro-l.3.S-triacrylyl-s-triazine,

150 parts of copper phthalocyanine pigment blue,

530 parts of water 1000 parts.

The printing designs obtained therewith show a very uniform, bluecoloration and are very fast to light and washing on cotton fabric andstaple rayon fabric.

Example 19 acetic acid solution of the basic 50 parts of a 10% aqueoussolution of the acetate of the basic polurea consisting of 0.05 mol ofdiethylene triamine, 0.95 mol of '-diaminodipropyl rnethylamine and 1.00mol of hexane diisocyanate are diluted 'with 10 parts of tylose(70:1000) and 200 parts of water.

Thereto are added parts of hexahydro-l.3.5-triacrylyls-triazi-ne and 24parts olf the pigment printing paste (IS-20%) and the mixture is made upwith water to '12 form 1000 parts. The resultant paste is applied to astaple rayon tfia'br-ic by slop padding.

After slop padding the material is (a) heated at C. for 5 minutes or (b)intermediately dried at about 50-60? C., or the excess water is removedby suction filtering and fixation is effected with alkalies, forinstance of sodium carbonate or sodium hydroxide solution of 38 B. (2-3grams per litre) at 4050 C. within about 7 seconds.

Slop-padding and fixation may be carried out continuously. The printingdesign obtained has a soft hand and very good fastness to rubbing.

Example 20 A printing paste of the following composition is applied to acotton fabric:

1000 parts.

After printing the fabric is subjected to the action of steam or reactedat 100 C. for 5 minutes. The printing designs thus obtained are ofexcellent uniformity and very fast to light and washing.

Example 21 A fabric of polyacrylonitrile is dyed in a padding solutioncontaining:

parts of a 10% acetic acid solution of the basic polyurea, which has aviscosity of 1000 centipoise (20 C.); the basic polyurea is obtained 'byreacting 0.05 mol of diethylene-triamine, 0.95 mol of ky diarninopropylrnethylamine and 1.01 mols of hexane diisocyanate,

5 parts of a 15 pigment dyestuff paste, 840 parts of water and 5 partsof hexahydro-1.3.S-triacrylyl-s-triazine.

1000 parts.

vAfter padding the material is dried and fixation is effected asdescribed in Example 24. The dyeing thus obtained has a soft hand andshows a very good stability to boiling sodium canbonate solution.

Example 22 92 parts (1 mol) of epichlorohydrin are introduced within 30minutes into the 55 C. hot solution of 48.3 parts mol) of.'y'-diaminopropyl rnethylamine HnN.CHz.CH2.CHz.N.CHz.CH:.CH:.NH: and500 parts of water Stirring at this temperature is continued until theviscosity has increased to about 200 centipoise; this is reached afterabout 4 hours. The solution is stabilized by addition of 25 parts ofconcentrated hydrochloric acid (25 B.).

After addition 'of water and pigment printing paste 100 C. for 10minutes. jifastness properties is obtained.

1000 parts.

After slop padding the material is dried and subsequently heated to 120C. for minutes. Dyeings are obtained, which are distinguished by verygood fastness to rubbing and crocking, to washing and to light.

Example 23 The printing paste containing:

200 parts of the 40% acetic acid solution of the reaction product ofpolybutyl acrylate and l-amino- S-methy-lamino propane,

200 parts of a 15% pigment dyestulf paste,

6 parts of adipic acid suspended in 50 parts of water, 300 parts oftragacanth thickening (65:1000), and 244 parts of water 1000 parts.

is printed on a cotton fabric.

After printing the fabric is dried and kept at 100 C. for minutes. Theprinting design thus obtained shows a good hand and good fastnessproperties.

In the above printing paste the free adipic acid can be replaced by it'ssalts, preferably those containing volatile bases such as ammonia.

Example 24 A printing paste containing: 250 parts of tragacanththickening (6521000), 400 parts of a 20% weakly acetic acid solution ofa basic polystyrene, 200 parts of a pigment dyestutf paste,

8 parts of adipic acid diamide and 142 parts of water 1000 parts.

is applied to a cotton fabric.

After printing the fabric is dried at 100 C. The printing design thusobtained is very fast to light and Washing.

Instead of the amide, the ester, for instance dimethylester, may beemployed in the above printing paste with equal success.

The basic polystyrene is obtained by reacting a copolymer of 90 parts ofstyrene and 10 parts of acrylic acid fluoride with 1-amino-3-methylaminopropane.

Example 25 A cotton fabric is printed with:

25 0 parts of polyethylene imine (50% 300 parts of methylcellulose (65:1000), 200 parts of a 15% pigment dyestufi paste, 175 parts of glacialacetic acid,

10 parts of hexamethylol melamine or its hexamethyl ether, 65 parts ofwater 1000 parts.

After printing the fabric is dried shortly and reacted at A printingdesign of very good Instead of hexamethyl melamine or its hexamethylether other cyanuric derivatives can be employed in the aboveprintingpaste with equal success.

. Example 26' The printing paste consisting of: 7

Example 27 15 parts of polyethylene imine (50%) are dissolved in threetimes the quantity of hot water, about 30 parts of tragacanth thickening(65 :1000) are introduced with stirring and the mixture is made up withwater to 500 cc. 10 parts of a 15 pigment dyestuff paste are mixed withstirring with 470 parts of water and poured into the above solution.Finally 25 parts of acetic acid (50%) and 5 parts of the reactionproduct of 1 mol of cyanuric chloride and 3 mols of ethylene imine,which correspond to the formula are added. Cotton fabric is dyed withthis padding mixture on the padding machine, subsequently dried andreacted at C. for 5 minutes. A dyeing of good uniformity and goodfastness properties is obtained.

We claim:

1. A textile printing paste comprising a pigment, a thickening agent, anaqueous solution of a salt formed from an acid and a resinous polyaminehaving recurring basic radicals selected from the group consisting ofprimary and secondary amino groups, and a polyfunctional compoundselected from the group consisting of epoxyhalogen-hydrines and alkylenedioxides, said basic radicals being the only groups in said resinouspolyamine capable of reacting with the polyfunctional compound.

2. A textile printing paste comprising a pigment, a thickening agent, anaqueous solution of a salt formed from a volatile acid and a resinouspolyamine having recurring basic radicals selected from the groupconsisting of primary and secondary amino groups, and a polyfunctionalcompound containing at least two substituents selected from the groupconsisting of epoxy-halogenhydrines and alkylene dioxides, said basicradicals being the only groups in said resinous polyamine capable ofreacting with the polyfunctional compound.

3. A textile printing paste as claimed in claim 2 wherein the resinouspolyamine is a basic polyamide.

4. A textile printing paste as claimed in claim 2 wherein the resinouspolyamine is a basic polyurethane.

A textile printing paste as claimed in claim 2 wherein the resinouspolyamine is a basic polyurea.

6. A textile printing paste as claimed in claim 2 wherein the resinouspolyamine is a basic polymer of an ester of an unsaturated aliphaticacid.

7. A textile printing paste as claimed in claim 2 wherein the resinouspolyamine is a basic polyurea obtained from hexamethylene diisocyanateand diethylenetriamine.

8. A textile printing paste as claimed in claim 2 wherein the resinouspolyamine is a basic polyurea ob- 15 tained from hexamethylenediisocyanate and 'y,'y'-diaminodipropyl-methylamine. V

9. Theprocessof decorating textiles which comprises applying to saidtextiles a printing paste as claimed in claim 1 and then rinsing saidtextiles in an aqueous solution of alkali torernove the acid constituentfrom the polymer salt contained in said paste.

10. The process of decorating-textiles which comprises applying to saidtextiles a printing paste as claimed in claim 2, and then heating saidtextiles to remove the volatile acid from the polymer salt contained insaid paste.

References Cited in the file of this patent UNITED STATES PATENTS Apr.26, 1949 Oct. 24, 1950 June 30, 1953 Nyquist et a1. Cupery Kleiner et al

1. A TEXTILE PRINTING PASTE COMPRISING A PIGMENT, A THICKENING AGENT, AN AQUEOUS SOLUTION OF A SALT FORMED FROM AN ACID AND A RESINOUS POLYAMINE HAVING RECURRING BASIC RADICALS SELECTED FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINO GROUPS, AND A POLYFUNCTIONAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF EPOXYHALOGEN-HYDRINES AND ALKYLENE DIOXIDES, SAID BASIC RADICALS BEING THE ONLY GROUPS IN SAID RESINOUS POLYAMINE CAPABLE OF REACTING WITH THE POLYFUNCTIONAL COMPOUND.
 9. THE PROCESS OF DECORATING TEXTILES WHICH COMPRISES APPLYING TO SAID TEXTILES A PRINTING PASTE AS CLAIMED IN CLAIM 1 AND THEN RINSING SAID TEXTILES IN AN AQUEOUS SOLUTION OF ALKALI TO REMOVE THE ACID CONSTITUENT FROM THE POLYMER SALT CONTAINED IN SAID PASTE. 